Lubricating composition



3,083,162 LUBRECATIN G COMPOSITION Franklin I. L. Lawrence, Bradford, Pa., assignor to Kendall Refining Company, Bradford, Pa., a corporation of Pennsylvania No Drawing. Filed Feb. 24, 1960, Ser. No. 10,559 13 Ciaims. (Cl. 252-33.4)

This invention relates to lubricating compositions and, more particularly, to lubricating compositions adapted to be added to gasoline fuels containing organolead, antiknock compounds prior to the injection of the fuel into the combustion zone of an internal combustion engine.

In an elfort to achieve maximum efiiciency in gasoline internal combustion engines, a large number of additives have been proposed to reduce the deposits which occur within the combustion zone. Included in this wide variety of additives are alkaline earth metal sulfonates having an excess of metal (commonly termed overbased sulfonates) and chlorinated hydrocarbons.

Alkaline earth metal sulfonates are added to base oils and the like to provide improved detergent properties. With the use of such highly basic materials, sludging, carbon formation and ring sticking are reduced. Certain additives of this class, however, contribute to the formation of undesirable combustion chamber deposits, thereby inducing spark plug fouling.

Additionally, it is known that chlorinated hydrocarbons function as lead scavengers when incorporated into lead-containing gasoline fuels. The chlorine of the chlorinated hydrocarbons reacts with the lead during combustion to produce volatile lead compounds which pass from the combustion chamber. During combustion, non-volatile lead compounds tend to form which become deposited on the internal surfaces of the engine and thereby adversely affect the operation of the engine.

While the art has succeeded in extending engine life and in improving engine efficiency, the quest for even more effective additives or combination of additives continues.

Therefore, it is a primary object of the present invention to provide a lubricating composition which provides extended engine life.

It is an additional object of this invention to provide I a lubricating composition adapted to be added to gasoline fuels prior to the injection of the fuel into m internal combustion engine.

It is another object of the present invention to provide a lubricating composition which promotes improved overall engine performance.

It is still another object of the present invention to provide a lubricating composition having excellent detergent properties.

t is a further object of the present invention to pro- *vide a lubricating composition which promotes im- 'proved spark plug performance. Broadly stated, the present invention embraces a lubricating composition comprising a major amount of lubricating oil and (a) about 2.5 to about 3.5 weight percent of an oil-soluble alkaline earth metal sulfonate having a metal ratio of at least 2.25 selected from the group consisting of calcium, barium and strontium sulfonates and (b) an amount of a chlorinated hydrocarbon sufiicient to provide between about 0.01 and about 0.015 equivalent of chlorine per 100 weight parts of lubricating composition.

The invention further contemplates a gasoline fuel containing the above defined lubricating composition.

While overbased sulfonates and chlorinated hydrocarbons are known additives, the conjoint utilization of these materials within the above defined critical limits has been found to produce a synergistic result. When, for example, either more chlorinated additive or less chlorinated States Patent and higher.

3,083,162 Patented Mar. 26, 1963 additive is employed, engine performance approximates that obtained employing other standard additives. When, however, the additives are employed within the critical ranges, engine performance is increased materially.

The alkaline earth metal sulfonates of the present invention embrace the oil-soluble alkaline earth metal salts of oil-soluble sulfonic acids which contain substantially more metal than is equivalent to the anionic radicals of the normal oil-soluble salts. The sulfonates generally useful in the invention are disclosed, inter alia, in Patents Nos. 2,616,904, 2,616,905, 2,616,906, 2,616,910, 2,616,- 911, 2,616,924, 2,616,925, 2,617,049 and 2,723,235 to Asseff et al. The metal sulfonates employed in this invention have a metal ratio of at least about 2.25. Sulfonates may be characterized by a metal ratio up to 4.5

As employed herein, the term metal ratio defines the ratio of equivalents of alkaline earth metal present in the sulfonate to equivalents of sulfonic acid groups. It will be apparent that the metal ratio of a neutral alkaline earth sulfonate is 1, and the metal ratio of a normal basic sulfonate (i.e.: RSO -CaOH) is 2.

The metals which form the sulfonates useful in the present invention are the alkali earth metals, strontium, barium and calcium. Calcium sulfonates are preferred for this invention.

The overbased sulfonates may be derived from sulfonic acids such as mahogany sulfonic acids; petrolatum sul' fonic acids; monoand polywax substituted naphthalene sulfonic, phenol sulfonic, diphenyl ether sulfonic, diphenyl ether disulfonic, naphthalene disulfide sulfonic, naphthalene disulfide disulfonic, diphenyl amine disulfonic, diphenyl amine sulfonic, thiophene sulfonic, alphachloro-naphthalene sulfonic acids, etc.; other substituted sulfonic acids such as cetyl chlorobenzene sulfonic acids, cetyl-phenol sulfonic acids, cetyl-phenol disulfide sulfonic acids, cetyl-phenol mono-sulfide sulfonic acids, cetoxy caprylbenzene sulfonic acids, di-cetyl thianthrene sulfonic acids, di-lauryl beta-naphthol sulfonic acids, and di-capryl nitro-naphthalene sulfonic acids; aliphatic sulfonic acids such as paraffin wax sulfonic acids, unsaturated paraflin wax sulfonic acids, hydroxy substituted paraflin wax sulfonic acids, tetraisobutylene sulfonic acids, tetraamylene sulfonic acids, chlorosubstituted paraflin Wax sulfonic acids, nitroso paraflin wax sulfonic acids, etc.; cycloaliphatic sulfonic acids, such as petroleum naphthene sulfonic acids, bis-.(diisobutyl)-cyclohexyl sulfonic acids, monoand poly-wax substituted cyclohexyl sulfonic acids, etc.

Preparation of the alkaline earth metal sulfonates of the present invention may be carried out by any of the methods known to the art. For example, the overbased salts may be prepared by combining an inorganic alkaline earth compound with an oil-soluble sulfonic acid and/ or the alkaline earth salt of the oil-soluble acid in the presence of a promoter, such as phenol. Such a method is exemplified inter alia in Assefi Patent No. 2,617,049. -In such a manner, overbased sulfonates may be prepared which exhibit metal ratios up to about 4.5.

Additional information concerning the preparation of organic metal complexes suitable for the present invention can be found in the patents listed above.

The chloro hydrocarbons contemplated for use in the present invention include monoand poly-chlorinated hydrocarbons which have a vapor pressure in the rangeof about 0.2 to about 6.0 mm. Hg at 50 C. These halogenated hydrocarbons include such chlorinated hydrocarbons as l-chloronaphthalene, 1,8-dichlorooctane, dichloroxylenes (mixed), 3,4-dichlorocumene, pentachlorobutanes (mixed), hexachloropropylene, 1,2,4-trichlorobenzene, dichloroheptanes (mixed), 2,4-dichlorotoluene, 1,2-dichlorocyclohexane and l-chlorooctane.

Preferred chlorinated hydrocarbons for utilization in the present invention consistitute chlorinated benzene and monoand poly-alkylated benzenes having from one to three carbon atoms in the alkyl chain and containing the chlorine attached to the benzene ring. Such compounds include, without limitation, chlorobenzenes, dichloroxylenes, monochloroxylenes, dichlorotoluenes, monochlorotoluenes, dichlorocumenes, monochlorocumenes, dichloroethyloenzenes, monochloroethylbenzenes, and the like. Dichlorotoluenes constitute a particularly preferred material for the practice of this invention.

The lubricating oil base useful in the present invention may be selected from any of the oils which find utility in lubricating compositions. They may be of vegetable, animal or mineral origin, but mineral oils, i.e., oils derived frompetroleum, are preferred for the present invention. The properties of the base oil will depend upon the particular-use and environment for which the lubricating composition is desired. M

The lubricating compositions of this invention contain from about 2.5 to about 3.5 weight percent and preferably from about 2.8 to about 3.2;weight percent of oilsoluble alkaline earth metal sulfonates and suflicient chlorinated hydrocarbonto provide from about 0.01 to about 0.015 equivalent of chlorine and preferably from about 0.012 to 0.013 equivalent of chlorine per 100 weight units of lubricating composition; I

It will be apparent that the base oil may contain other additives to improve such properties asthe oiliness, pour point, and cold test without departing from the scope or spirit of the invention, s 1 7 s The components of the invention may be mixed by any method-known to the art and in any sequence. The invention is not intended to be limited by the method of mixing the additive and the base oil. v v s I The lubricating compositions of the present invention are ideally suited for use in engines wherein the lubricant is added with the gasoline fuel, such as, for example, I

two-cycle gasoline engines. Outboard motors, power saws, power mowers and the like constitute typical examples of equipment which may employ a two-cycle gasoline engine. a

. The fuel employed in the tests was a mixture of thermally cracked and 60% catalytically reformed gasoline containing 2.95 ml. tetraethyl lead, and characterized by the following properties:

Gravity APL- 57.4 Reid vapor pressure pounds 9.8 Distillation range F 97-403 Research octane number 93.3

The oil-to-gasoline ratio was maintained at l pint to 2 gallons.

The engine was operated until a spark plug fouled, as evidenced by a decrease of about at least 300 r.p.m. in the speed of the engine or an intermittent misfiring of the engine. All spark plugs then were changed. The test was terminated when three spark plugs had fouled.

The engine was disassembled and rated at the end of the test. Piston and port deposits and ring sticking were evaluated. The more important factors were Weighted in a summation of merit ratings. A weighted total merit rating of 100 denoted a perfectly clean engine.

Since the total test time varied because of variations in spark plug life, an overall measure of performance was employed which acounted both for engine cleanliness and for the test time. Weighted total merits were multiplied by total test time to provide a merit-hour rating. The merit-hour rating reflects good spark plug performance (long test in hours), as well as the ability of the oil to keep the engine clean.

Lubricating Composition of This Invention A lubricating composition was formulated which contained 3 weight percent of an overbased calcium sulfonate, 1% dichlorotoluene and 96% base oil.

The overbased calcium sulfonate analyzed 3.48% calcium, 2.34% sulfur and was characterized by a specific gravity of 1.00. The metal ratio of the calcium sulfonate was about 2.38.

The lubricating compositions of this invention'most appropriately may be employed in conjunction with gasoline fuels containing organolead anti-knock additives, such as tetraethyl lead, vtetramethyl lead and the like.

of this. invention may be any of the leaded fuels of the gasoline rangewhich find utility asfuels for internal cornbustion engines. Leaded gasolines are well-known to the art-and, generally, contain from about /2 to about 4 or 5 cc; of tetraethyl lead per gallon of gasoline.

' The lubricating composition of this invention may be employed in any desired amount inthe gasoline. Normally, the lubricating compositions will be employed in amounts from about A to about 1 pint per gallon. of gasoline, andpreferablyfrorn about /3 to about /3 pints per gallon of gasoline. Blending may be efiected in any desired manner. A V

The following specific embodiments are. included for illustrative purposes only and in no way are intended to limit the scopeof the invention.

EXAMPLE I V Test'Procenlure I ,The following procedure was. employed to evaluate the high temperature-high speed performance characteristics of lubricating compositions: d d A four-cylinder, 40 -brake horespower gasolineengine (Mercury Mark 55) was operated at a speed of 5250i-50 r.p.m., with a jacket outlet temperature maintained at 110-115 F. The engine was operated at full throttle with a load disk instead of a propeller; The load mately 40 b.h.p. at the 5.250 r.p.m.1of the engine. 7

The gasoline fuels useful with the lubricating composition 7 disk was designed to absorbthe rated load of approxi-J The dichlorotoluene was characterized as follows:

Molecular weight 198 Boiling range 185-209 C./730 mm. Hg 51-53% chlorine The amount employed provideda chlorine content of 7 about 0.0125 equivalent of chlorine per 100 weight parts pane dewaxed and phenol extracted to a 'ratfinate yield. The oil was characterized by the following properties: V

Viscosity at F., SUS 456 Viscosity at 210 F., SUS 61.7 Viscosity index 99.8 Pour point, F +10 Flash point, "P" W 480 Fire point, F 545 Carbon residue, percent 0.19 Gravity, API 29.3 The performance of the engine utilizing gasoline containing this additive is tabulated in Table 1 below,

7 V TABLE 1 e a 7 Test No, l Weighted total merits 77.87 Total time' 182:00 Merit-hours 14,063 Test time on plugs: 1 r v '0 11st set 101:20 Znd lset 44:15 3rd set 36:25

5 EXAMPLE 11 In order to demonstrate the eifect of the overbased calciurn sulfonate employed as a sole additive to the lubricating oil, two tests were conducted employing 2 weight percent of the overbased calcium sulfonate described in Example I above. In all other respects, the tests were identical with those described in Example I above.

The results of these tests are reflected in Table 2 below.

TABLE 2 Test N o.

Compounding data:

' 98. 98. 0 2. 0 2. 0 81. 51 85. 00 63:20 37:20 Merit-hours 5, 162 3, 173 Test time on plugs:

1st set 26:20 33:20 15:10 3:10 21:50 0:50

EXAMPLE III In order to demonstrate the eflect of the dichlorotoluene employed alone, 2 Weight percent of the dichlorotoluene were admixed with the base oil of Example I. The results of the test wherein the lubricating composition contained approximately 0.025 equivalent of chlorine per 100 weight parts of lubricating composition are reflected in Table 3 below.

TABLE 3 Compounding data: Test No. 4 Base oil 98.0 Additive, dichlorotoluene 2.0 Weighted total merits 68.46 Total time 80:00 Merit-hours p 5477 Test time on plugs:

1st set 51:35 2nd set 15:40 3rd set 12:45

EXAMPLE IV In order to demonstrate the optimum range of overbased sulfonate and chlorinated hydrocarbon, tests similar to Example I were conducted employing the same lubricating composition ingredients, but varying amounts of dichlorotoluene. The data from these tests is reflected in Table 4 below. In test No. 5 the chlorine content of the lubricating composition was about 0.00625 equivalent per 100 Weight units of lubricating composition and the chlorine content in test No. 6 was about 0.025 equivalent of chlorine per 100 weight units of the lubricating composition.

TABLE 4 Test No.

Compounding data:

Base oil 96. 5 95. 0

3.0 3.0 0.5 2. 0 83.28 80.00 72:20 48145 Merit-hours 6024 Test time on plugs:

1st set 60:35 I 48:45 2nd set 9:05 3rd set 2:40

1 Terminated at drive train gear failure.

While drive train gear failure terminated test No. 6 at the end of 48 hours, the Weighted total merits of that test make it apparent that the lubricating composition therein employed was substantially less efficient than that exemplified in Example I'II above,

EXAMPLE V In order to demonstrate further the eifectiveness of the lubricating compositions of this invention, two commercial outboard motor oils were employed in the test procedure described in Example I. Oil A was a naphthenic distillate and contained no apparent additives and Was characterized by the following properties:

Viscosity at 210 F., SUS 59.6 Viscosity at 100 F., SUS 763 Viscosity ind x 1.0 Pour point, F +5 Flash point, F 420 Fire point, F 465 Oil B was a solvent refined oil containing overbased barium sulfonate and zinc dithiophosphate additives. Its properties were characterized as follows:

Viscosity at 210 F., SUS 62.6 Viscosity at 100 F., SUS 476 Viscosity index 99 Pour point, F- 25 Flash point, F 445 Fire point, F 495 Sulfur, percent 0.55 Phosphorous, percent 0.03 Barium, perc nt 0.125 Zinc, percent 0.04

The results of the tests conducted employing oils A and B are reflected in Table 5 below. The data from test No. 8 particularly reflect the tendency of certain detergent additives with appreciable metal content to promote spark plug fouling.

TABLE 5 Test N0.

7, oil A 8, oil B EXAMPLE Still further to demonstrate the etfectiveness of the additive of this invention, tests were conducted employing the base oil identified in Example I, free of additives.

The results of these tests are reflected in Table 6 below.

efiiciency in the tests described in Example I. The results of these tests are reflected in Table 7 below.

TABLE 7 Test No.

Compounding data:

Base oil Additiv G--- 0.8 Weighted total merits. 66. 69 73. =17 66. 30 91.29 Total time 32:45 :45 35:00 11:20 54:20 49:30 26:15 31:35 Merit-hours 2. 563 2, 343 2, 061 984 3, 023 3, 537 1, 740 2, 883

Test time on plugs:

1st set 24:45 21:30 25:30 5:05 :50 28:30 18:00 23:00 2nd set- 7:50 3:50 4:50 2:10 17:20 12:00 8:00 5:50 3rd Set..- :10 0:25 4:40 4:05 6:10 9:00 0:05 2:45

The above lettered additives are identified as follows:

Additive Chemical composition Properties A Low molecular weight poly- 5.3% nitrogen, 1.7% phosmethacrylatecontainingnitro'. phorous.

gen functional groups plus a phosphorous extreme pressure agent. B Lead alkyl phenate 16.%1le%d, specific grav- 1 y C P185, terpene reaction product.-- 4.7% phosphorous, 13.0% sulfur, 1.02 specific gravity. 7 Y D .Bis-B-chloroethyl vinyl phos 29.5% chlorine, 13.3%

p onate. :phosphorous. E Tricresyl phosphate"; 8.4%phosphorous, moler cular Weight 368. F 4,4-methylenebis (2,6-di-tert.-.

butyl phenol). G Sorbitolrnonooleate Specific gravity 1.00.

It will be apparent that the gasolines to which the additives of this invention have been added may contain other standard additives well-known to the art.

Since modifications of the present invention will be ap 'mm'to those skilled in the art, the invention is intended to be limited only by the scope of the appended claims.

I claim: H V U H 1. A lubricating composition comprising a major amount of lubricating oil and (a) from about 2.5 to about 3.5 weight percent of an oihsoluble alkaline earth metal sulfonate having'a'hietal to's'ulfonic acid 'group' equivalent ratio of at least 2.25 selected from the "group consisting of calcium, barium, and strontium sulf onates and (b) an amount of achlorinated hydrocarbon selected from the group consisting of monoandpoly-chlorinated hydrocarbons having-a vapor pressure in the range of about 0.2 to about 6.0 mm. ofniercury at 50 C. sulficient to provide between about 0.01 and about 0.015 equivalent of chlorine per 100' weight parts of lubricating composition. w r

2. The lubricating composition of claim 1 wherein the metal sulfonate is present in amounts from about 2.8 to about 3.2 weightpercent. a

3. The lubricating-composition of claim lwherein the chlorinated hydrocarbon is present inamounts suificient to provide between about 0.012 and 0.013 equivalent of chlorine per 100 'weight units of lubricating composition.

4. The lubricating composition of claim 1 wherein the V sulfonate is present in amounts from about 2.8 to about 3.2 weight percent and the chlorinated hydrocarbon is present in amounts sutficient to provide between about 0.012 and 0.013 equivalent of chlorine per 100 weight units of lubricating composition.

5. The lubricating composition of claim 1 wherein the chlorinated hydrocarbon is selected from, the group consisting of chlorinated benzene and monoand poly-alkylated benzenes having from 1 to 3 carbon atoms in the alkyl chain and containing the chlorine attached to the benzene ring.

6. The lubricating composition of claim 1 .wherein the alkaline earth metal sulfonate is a calcium sulfonate.

7. A lubricating composition comprising a major amount of lubricating oil and (a) from about 2.5 to about 3.5 weight percent of an oil-soluble calcium sulfonate having a metal to sulfonic acid group equivalent ratio of about 2.38 and (b) dichlorotoluene in an amount sufficient to provide between about 0.01 and about 0.015 equivalent of chlorine per 100 weight parts of lubricating composition. v v

8. A leaded gasoline containing a lubricating amount of a lubricating composition comprising a major amount of lubricating oil and (a). from about 2.5 to about 3.5 weight percent of an oil-soluble alkaline earth metal sulfonate having a metal to sulfonic acid group equivalent ratio of at least 2.25 selected from the group consisting of calcium, barium, and strontium sulfonates and (b) an amount of a chlorinated hydrocarbon selected from the group consisting of monoand poly-chlorinated hydrocarbons having a vapor pressure in the range of about 0.2 to about 6.0 mm. of mercury at 50 C. sufiicient to provide between about 0.01 and about 0.015 equivalent of chlorine per 100 weight parts of lubricating composition.

9. The leaded gasoline of claim 8 containing from about A to about 1 pint of lubricating composition per gallon of gasoline.

10. The leaded gasoline of claim 8 containing from about A to about pint of lubricating composition per gallon of gasoline.

11. A leaded gasoline containing a lubricating amount of ;a lubricating composition comprising a major amount of lubricating oil and (a) from about'2.5 to about 3.5 weight percent of an oil-soluble calcium sulfonate having a metal to sulfonic acid group equivalent ratio of about 2.38 and (b) dichlorotoluene in an amount sufiicient to provide between about 0.01 and about 0.015 equivalent of chlorine per 100 weight par-ts of lubricating composition.

12. The leaded gasoline of claim 11 containing from about% 'to about 1 pint of lubricating composition per gallon of gasoline.

13. The leaded gasoline of claim 11 containing from tabout /a toabout /a pint of lubricating composition per gallon of gasoline.

- References Cited in the file of this patent 7 UNITED STATES PATENTS 

1. A LUBRICATING COMPOSITION COMPRISING A MAJOR AMOUNT OF LUBRICATING OIL AND (A) FROM ABOUT 2.5 TO ABOUT 3.5 WEIGHT PERCENT OF AN OIL-SOLUBLE ALKALINE EARTH METAL SULFONATE HAVING A METAL TO SULFONIC ACID GROUP EQUIVALENT RATIO OF AT LEAST 2.25 SELECTED FROM THE GROUP CONSISTING OF CALCIUM, BARIUM, AND STRONTIUM SULFONATES AND (B) AN AMOUNT OF A CHLORINATED HYDROCARBON SELECTED FROM THE GROUP CONSISTING OF MONO- AND POLY-CHLORINATED HYDROCARBONS HAVING A VAPOR PRESSURE IN THE RANGE OF ABOUT 0.2 TO ABOUT 6.0 MM. OF MERCURY OF 50*C. SUFFICIENT TO PROVIDE BETWEEN ABOUT 0.01 AND ABOUT 0.015 EQUIVALENT OF CHLORINE PER 100 WEIGHT PARTS OF LUBRICATING COMPOSITION. 